DE2058563A1 - Stabilized iron chelates and plant treatment compositions containing them - Google Patents

Description

Dr. F. Zumsteln ten. - Dr. E. Assmann Dr. R. Koenigsberger - Dlpl.Phys.R. Timber construction?

Dr. F. Zumstein jun. Patent attorney

8 Munich 2, Bräuhautstroß 4 / III

Case 2-3218 / PR θ68

Stabilized iron chelates and plant treatment compositions containing them

The present invention relates to compositions based on ferric complexes (iron chelates), which by adding Compounds that belong to the chemical class of hydroxybenzophenones are stabilized.

The role that iron plays in the physiology of plants is very important. So this element plays a catalytic role in converting leukophyll to chlorophyll. -A pulpit of iron leads to a decrease in the plants Amount of chlorophyll, which is manifested by the progressive disappearance of the green color of the plants. This disease, which one calls Eisenmarigel chlorosis, leads when it is very pronounced is to cause the foliage to fall off and then to halt the growth of the infected plant.

Means for combating this disease are therefore of great importance for the cultures - these means are based on a supply of iron that can be assimilated by the roots or leaves, the sprinkling or spraying of usual elsenic salts, such as, for example! Like sulphate, it has a very slight and little lasting effect. In addition, these salts sometimes cause harm. Hart gets the best results when using organic

J 109824/2301

Complexes of iron, such as the chelates, in which the iron is strongly bound and which are absorbed by the plants, can be without damaging theeas au.

The most effective complexes currently known are those described in French patent specification 1,161,196. These are derivatives of ethylenediamino-bis-hydroxyphenyl-acetic acid). Among these, the best known are the Perrichelates of the _{ethylene diamino-N i} N ^t -bis- [oC ~ (2-hydroxyphenyl) -esslgic acid] and the ethylenediamino-N _i N) -bis * -bC- (2 -hydroxy-5-methylphenyl} acetic acid] in the form of its sodium salts.

These complexes are referred to below with the abbreviations EDDHA / Pe and EDBHMA / Pe. They are chemically very stable, yes are they against certain factors, such as exposure to light; not permanent, which they break down and make them progressively inactive. This disadvantage is particularly noticeable when ■ the compounds are in solution, making their use in this form difficult or even impossible. Different Known stabilizers have been used to protect the above chelates tried, but to no avail. The mixtures of chelates with these stabilizers decompose very quickly in aqueous solution, even with proportions of stabilizer from 25 to 50 #, based on the weight of the chelate.

It has now been found that a certain class of hydroxybenzophenones a surprising result when used in ordinary concentrations Stabilization effect against a deterioration of influences, such as those of light, climate and similarly, when they are added to certain iron chelates.

The present invention therefore particularly relates to the use of hydroxybenzophenones of the formula

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: "-." ¹¹¹¹ I "!: - '··;■' ■■ /""■ ■ ': J?

—0 -! - O

II

for stabilization, of ferric complexes of the following probable formula

p /% ο

The use can be realized in the form of solid and liquid compositions, one or more ferric complexes of the formula I in an amount of about 0.01 to 80 wt -.% For the former and about 0.01 to 20 wt .- $ of the latter contain one of the hydroxybenzophenones of the formula II in an amount of 0.02 to 10 %}, preferably 0.2 to 2%, of the weight of the complex or complexes of the formula I, the solid compositions being at least partially soluble in water , while the liquid compositions are at least partially aqueous.

In formula I, Rj, R ^, R ^ and R ^, which can be the same or different from one another, ^{mean 3 ewe} ü ^{s Θ} * ^η hydrogen atom or an AHeyI radical with 1 to 5 carbon atoms or a hydroxy alky Ires t with 1 to 3 Carbon atoms, where R, and R ₂ , also together an alkylene group with 3 to 6 carbon

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2056563

atoms, in particular a tetramethylene group, Χ » to Xo *, which can be the same or different from one another, each denotes e„ in hydrogen atom or an alkyl radical with 1 to 12 carbon atoms or a group OH, NO ₂ or CN or an alkoxy group with 1 to 8 carbon atoms, or a chlorine, bromine or «iodine atom or a group -COOM or -SO ₅ M or a group

in which Y ^ a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms or a hydroxyalkyl radical with 2 to 4 carbon atoms or an alkanoyl or alkenoyl radical with a maximum of ß carbon atoms, while Y _{g represents} a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms or represents a hydroxyalkyl radical having S to 4 carbon atoms, where X | to Xg are preferably chosen so that the two aromatic parts of the molecule are symmetrical and where X «to Xd preferably denote hydrogen atoms and / or methyl radicals, and M and M ^", which can be the same or different from one another, each denote a hydrogen atom or a Alkaline cation or a cation of the formula

in the t

and

which are the same or separate from one another

* can each represent a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms or fine hydroxyalkyl radical with 2 bin k carbon atoms, whereby Y * and Y ^ together with the nitrogen atom "are bonded to the" a pyrrolidino, piperidino, morpholine * i-piperazino or 4-methyl-1-piperazino radical can be added.

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\ \ In the formula II the different symbols have the following

< \ interpretations *

\ R denotes a hydrogen atom or a hydroxyl group or an alley group with 1 to 8 carbon atoms,

^ R 'represents a hydrogen atom or a chlorine atom or a (An alkyl radical with 1 to 5 carbon atoms or an O group M represent

i R "means a hydrogen atom or a chlorine atom or a

* Hydroxy group or an alkyl radical with 1 to 5 carbon ^; atoms or an alkoxy group with 1 to 8 carbon atoms *

; or a group COOM, "

R ^"1 represents a hydrogen atom or a chlorine atom or a _'x hydroxy group or an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Constitute and

¹ IV

} R denotes a hydrogen atom or an alkyl radical with 1 to

1. 5 carbon atoms j where

j H has one of the meanings given in connection with the formula I,

(Dir balance of the composition, if such is present, j [consisting essentially of an ode ^ more products of y class of fertilizers, insecticides, fungicides, nematocides, Bak-1 ttrizide, obe? Surfactants., Compounds which inhibit the Pflän- | «n S | iurenelei (iente out, and, öaunßßvermit celebration" the $!

solid composition Ip water to favor

Dissolution of the

like, with the remainder in the case of the liquid compositions can consist of filistic or partial water.

fi} | or more of these ingredients can be used in the invention Composition in the appropriate amounts to achieve the desired | # Effect to; receive, be present «They should be chosen that they on the one hand with each other and on the other hand with

4 # n ferric complexes and stabilizers are contractual «

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Among the ferric complexes included in the compositions of the invention may be present, one can use the Sodium, potassium, ammonium, diethylamine, diethanolamine and Morpholine salts of those formed with the acids listed below Name ferrichelates:

1,2-bis- (2-hydroxy-1-4 -carboxybenzylaraino) -ethane (a) 1,2-bis- (2-hydroxy-5-methyl-ot-carboxybenzylamino) -ethane (b) 1,2-Bi s -ι (2-hydroxy -3-methy 1 - oC -carboxy benzy lamino) -ethane 1,2-bis- (2-hydroxy-4-methyl-ol-carboxybenzylamino) -ethane 1,2-bis ( 2-hydroxy-3,5-dimethyl-oC-carboxybenzylamino) -ethane 1,2-bis- (2-hydroxy-5-tert-butyl-ot-carboxybenzylamino) -ethane 1,2-Bi5- (2 -hydroxy-5-octyl-06-carboxybenzylamino) -ethane 1,2-bis- (5-chloro-2-hydroxy-od-carboxybenzylamino) -ethane 1,2-bis- (5-bromo-2-hydroxy-ol -carboxybenzylamino) -ethane i, 2-bis- (j}, 5-dichloro-2-hydroxy-oc-carboxy benzy lamino) -ethane 1,2-bis (3 t 5-dibromo-2-hydroxy- d - carboxybenzylamino) ethane 1,2-bis (2-hydroxy-5-iodine d -carboxybenzylamino) ethane 1,2-bis (5-oarboxy-2-hydroxy- oi-carboxybenzylamino) ethane 1,2- Bis- (5-cyano-2-hydroxy-oC-carboxybenzylamino) -ethane 1,2-bis- (2,4-dihydroxy-od-carboxybenzylaraino) -ethane 1,2-bis- (2-hydroxy-5-sulfo -06-carboxybenzylamino) ethane 1,2-bis (2-hydroxy-5-nitro-oC-carboxybenzylamino) ethane 1,2-Bi s- (2-hydroxy-4-methoxy- OC-carboxybensylamino) -ethane 1,2-bis- (2-hydroxy-4-hexyloxy-οί, -carboxy benzylamino) -ethane 1,2-bis- (2 -hydroxy-o6-carboxybenzylamino) propane i, 2-bis- (2-hydroxy-oil-carboxybenzylamino) -butane 2,3-bis- (2-hydroxy-oC-carboxybenzylamino) rbutane "1,2-bis- ( 2-hydroxy-ot-carboxybenzylamino) -eyelohexane i, 2-BiS "(2-hydroxy-O6-carboxybenzylamino) -4-hydroxy-butane

(a) The salts of this perric complex are known as ferric chelates of ethylenediamino-N, N ^f -bis- [a- (2-hydroxyphenyl) acetic acid]; the sodium salt is referred to here with the abbreviation EDDHA / Fe.

(b) The salts of this ferric complex are dec designation

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;. · Ferrichelate the

phenyl) acetic acid] known * the Hatrum salt is here with the Abbreviation EDDHHA / Fe.

"Among the stabilizers used according to the invention, ftan give the following examples as examples:

2-hydroxy-benzophenone
2-hydroxy-4-methoxy-benzophenone. 2-Hydroxy - ^ - methoxy-5-sulfo-benzophenone 5-chloro-2-hydroxy-benzophenone 2-hydroxy-4-biethoxy-4'-methyZ-benzophenone 2-hydroxy-5-methyl-benzophenone 2-hydroxy-4 '-methy 1-benzophenone 2-hydroxy -4 * - & thyl-benzojphenoif 2,2 * -dihydroxy-benzophenone 2 _# 4-dihydroxy-benzophenone 8,2 * -dihydroxy-4-methoxy-benzophenone 2,2'r-dihydroxy- 4 , h * -dimethoxy-benzophenone

2, ¹ J-dihydroxy-4 * -methyl-benzophenone,

2,4-dihydroxy-4 * -methoxy-benzophenone 2, K -dihydroxy -h * -äthy1-benzophenone 2,2'-dihydroxy-4,4 * -dimethoxy-5-sulfo-benzophenone (sodium salt) 2,4, 4'-Trihydroxy-benzophenone 2 1 2 *, h, k * -Tetrahydroxy-benzophenone 2, k -Dihydroxy -4 '-oct y loxy -benzophenone 2,2'-Dihydroxy-4-octyloxy-benzophenone 2 # 2'- Dihydroxy-3-raethyl-benzoiÄienon 2 , 4-Dihydroxy-2'-carboxy-benzophenone (sodium salt) 2,2 * -Dihydroxy-4'-chlorobenzophenone 2,2'-Dihydroxy-5-chloro-4,4 * -dimethoxy-benzophenone.

'* The icoiaraeimen Hydroxy-benzophenone are easily through Implementation of benzoic acid or its homologues with the appropriate ones Obtained phenols. Lewis acids such as aluminum chloride or boron fluoride, are excellent catalysts for

. that kind of reaction. These procedures are in the literature

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(cf. in particular Ber. 1897 »29_, 971» Org. reactions, 1949, a> 287 J BuI. Soc. Chirn. 1952 * page 501 J. Org. Chem. 1954,

It should be noted that the stabilizers according to the invention are free of any toxicity to plants, which is essential for their usefulness.

It was also unexpected that these hydroxy-benzophenones would be theirs stabilizing properties in the presence of alcohol, as present in the preferred compositions according to the invention because it is known that benzophenone undergoes photochemical reduction in the presence of alcohol learns that it denatures.

In the following some attempts are described to the effectiveness to show these stabilizers.

Attempt I.

There were various proportions of chelate EDDHA / Pe in distilled Dissolved water, and the resulting solutions were dispensed into colorless glass bottles. There was 100 g of solution in each bottle and the bottles were hermetically sealed.

The bottles were placed in a cabinet made of polished aluminum, inside of which a 700 watt mercury vapor high pressure discharge lamp was installed, which largely reproduces the solar spectrum from 2800 to 7600 Å. The internal temperature of the cabinet was kept ^{at about 50 ° C. during the entire duration of the experiments.}

A spectrophotometric determination of the chelate EDDHA / Fe in each bottle was carried out at periodic intervals, working at a wavelength in the vicinity of 490 η \ μ , which corresponds to an absorption maximum of the chelate EDDHA / Fe in solution.

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The results obtained are shown in the table below. The values are expressed in % chelate based on a non-irradiated comparison of the same concentration.

concentration
to EDDHA / Fe 40 Exposure time 80 ; (in hours) 120 88 60 76 100 70 71 80 62 73 55 2 # 65 64 48 57 30th 0.5 % 38 - 58 40 mm 0.05 % 0

The results show that the EDDHA / Fe chelate is taking in solution. the experimental conditions and especially in less concentrated Solution is fickle.

Experiment II

Different solutions of the ghelate EDDHMA / Pe in distilled V / water prepared and brought under the conditions described in experiment I.

The spectrophotometric determinations were carried out at a wavelength in the vicinity of 505 m / 4, which corresponds to an absorption maximum of the CJie_lats EDDHMA / Fe in solution. The results obtained are given in comparison to a non-irradiated comparison sample of the same concentration »

concentration
to EDDHMA / Fe 20th Exposure time 6o (in hours) 180 0.5 * 93 40 «. 120 ■ 72 0.1 % 92 90 - 88 30th 0.05 % 66 68 40 41 12th 0.02 % 76 - 26th 22nd IN THE - 0

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These results indicate that the chelate EDDHMA / Pe in solution / under the experimental conditions, albeit to a lesser extent

Dimensions than the chelate EDDHA / Fe, and also here in particular in . less concentrated solution is inconsistent.

Trial III

An aqueous-alcoholic solution (60% by volume, ~ $ ethanol and 40% by volume of water) with a content of 0.1 % chelate EDDHA / Fe was prepared and bottled as described in Experiment I. 500 ppm (parts per million) of a stabilizer according to the invention was added. These are labeled as follows}

A: 2,2 ', ^, V-tetrahydroxy-benzophenone Bi 2,2'-dihydroxy _i 4,4 ^l -dimethoxy-benzophenone Cj 2-hydroxy-4-methoxy-benzophenone D: 2,4-dihydroxy-benzophenone

It sodium salt of 2,2-dihydroxy-4 _J 4 ^{t i} -dimetlioxy-5-sulfobenzophenons.

At the same time, a number of other comparable bottles, containing the same solution without stabilizer.

This comparative series was designated with the letter X.

The bottles so produced were placed in the irradiation device described in Experiment I, and the spectrophotometric Determinations were made after 120 hours of exposure under the same conditions as indicated in experiment I.

The same experiments were carried out using a proportion of 250 ppm of each stabilizer.

The results obtained are shown in the table below (the values are expressed relative to a comparison, as in the case of the Versuoh!).

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Type of
Stabilizer Concentration of stabilizer 250 ppm A.
B.
C.
D.
E.
X '500 ppm 77
39
53
59
30th
0 84
42
62
70
^ 3
ö

These results show that the compounds of the 2-hydroxybenzophenones class are effective in protecting the EDDHA / Fe chelate.

- Experiment IV

Aqueous solutions with 0.5 # and 0.05 # chelate EDDHA / Fe which were divided into several parts. These were with 2,2 ', 4,4'-Tetrahydroxybenzophenon in different proportions added and filled into bottles, which were placed in the irradiation device described in Experiment I.

The spectrophotometric determinations were carried out at periodic intervals. The results are in the following Table specified:

concentration
to EDDHA / Fe

Exposure time (in hours)

40

80

100

120

1*. Concentration of 2,2 ', 4,4'-tetrahydroxy-benzophenone: 10000ppni

0.5 %
0.05 %

92 94

84 88

80 87

79 85

2. Concentration of 2.2 *, 4.4 ^l -tetrahydroxy-benzophenone: 500 ppm

0.5
0.05

89 90

85 88

81 83

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- 40 12 - 2058563 ■ - 71 70 concentration
to EDDHA / Fe at 2.2 ' Exposure time (in hours) , 4,4'-tetrahydroxy-benzophenone: 10 ppm - J5. concentration 95 60 80 100 120 85 78 0.5 % 79 , 4,4'-tetrahydroxy -benzophenone: 100 ppm 40 34 0.05 % at 2.2 ^! 90 77 62 4. Concentration 86 67 58 0.5 % 43 0.05 %

Experiment V

The procedure was exactly as in the previous experiment, except that the tetrahydroxy-benzophenone was replaced by 2-hydroxy-4-methoxy-benzophenone in the same concentrations was replaced, the water was due to an ethanol / water mixture (60: 4o) the insolubility of this benzophenone in water. The results obtained are given in the table below:

concentration
to EDDHA / Fe concentration at Exposure time (in hours) 120 1. 0.5 % 40 60 80 100 1000 ppm 0.05 % 2-Hydroxy-4-methoxy-benzophenone: 84 concentration 97 97 95 94 54 Z. 0.5 % at 85 76 74 70 500 ppm 0.05 % 2-Hydroxy-4-methoxy-benzophenone: 85 concentration 97 95 94 88 73 ?. 0.5 % 91 87 81 75 100 ppm 0.05 % 2-Hydroxy-4-methoxy-benzophenone: 78 concentration at 96 95 87 86 - 4th 0.5 pounds 78 60 51 46 : 10 ppm 0.05 % 2-hydroxy-4-methoxy - «-" benzophenone 76 95 94 87 81 - 50 Ah

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Experiment VI

The procedure was as in experiment IV, but this time however 2,4-dihydroxy-benzophenone was used. The water was replaced by an ethanol / water mixture (40; 6o). The results are given in the table below:

concentration
to EDDHA / Fe. concentration at Exposure time (in hours) 40 60 80 96 94 94 91 89 97 89 76 100 120 1. 0.5 # 2,4-dihydroxy benzophenone 89 87 84 79 61 56 - : 1000 ppm 0.05 # 97 2,4-dihydroxy benzophenone 2,4-dihydroxy benzophenone 2,4-dihydroxy benzophenone 83 83 concentration 90 95 94 91 82 2. 0.5 % 87 70 43 : 500 ppm 0.05 % at 85 83 concentration 70 3- 0.5 % : 100 ppm 0.05 # 80 77 concentration 46 4th 0.5 # at * 10 ppm 0.05 % 76 74 at

Experiment VII

The procedure was as in Experiment IV, except that the sodium salt of 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfo-benzophenone was used. The EDDHA / Fe chelate was used in an amount of 0.05 % . The results are given in the table below: · ■

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Concentration.
to stabilizer 40 Exposure time (in 80 100 Hours) 1000 ppm 83 60 65 52 120 500 ppm 73 74 53 40 45 100 ppm 56 66 14th - 30th 38 -

The results of the last four trials compared to those of the first experiment, show the high degree of protective effect that the stabilizers according to the invention for the compositions who have the ferric helate of ethylenediamine-N, N-bis- [et- (2-hydroxyphenyl) acetic acid], which is called EDDHA / Pe here.

Experiment VIII

The procedure is as in Experiment IV, except that aqueous solutions of the EDDHMA / Fe chelate are used in a concentration of 0.05 and $ 0.02 used. The stabilizer used was the same, i.e. 2,2 *, 4,4'-tetrahydroxy-benzophenone in amounts of 250 and 100 ppm. The results are given in the table below.

concentration
to EDDHMA / Pe concentration
0.09 ■%
0.02 % at 20th Exposure time (in hours) 1. concentration
$ 0.05
0.02 % at 2.2 '
94
88 60 120 180 2. 8MCh IX 2.2 '
89
86 , 4,4'-tetrahydroxy
82 60
64 37 -benzophenone: 250 ppm
34
7th , 4,4'-tetrahydroxy-benzophenone 100 ppm
64 55 38
50 22 4

It was worked as in Experiment IV, where aqueous solutions

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gene of the chelate EDDHMA / Fe with a concentration of 0.05 and 0.02 % and as a stabilizer 250 ppm of a mixture of 2,2 ', 4,4'-tetrahydroxy-benzophenone and 2,2 ^f -dihydroxy-4,4 * -dimethoxy-benzophenone, available commercially under the trade name ¹¹ UVIMUL 490 "from General Aniline & Film Corporation, New York.

The results are compiled in the table below.

concentration
to EDDHMA / Fe Exposure time (in hours) 0.05 %
$ 0.02> . 20 60 120 lßo 9t 69 37 23
88 39 31 8

The results of these last two trials compared to those of the second experiment, show that the stabilizers according to the invention the ferric chelate of Ä'thylenediamino-N, N'-bis- | bC- (2-hydroxy-5-räethylphenyl) acetic acid], here EDDHMA / Fe is said to protect effectively in the compositions containing it.

The following are some examples of stabilized compositions given to further explain the invention "These examples do not represent any restriction. In particular, the named chelates EDDHA / Fe and EDDHMA / Fe by other ferric complexes, in particular by those mentioned above.

Examples 1 to 12

For the treatment of vegetable and fruit crops (especially types of lettuce, Beans, tomatoes, cucumbers and strawberry bushes), fruit trees (especially orange trees, apple trees, pear trees and apricot trees) and ornamentals compositions determined by spray application to foliage; the values give the Weight percentage rates with the remainder to 100> m; s. Water that

• 4 _r

is used as a solution, · .. · :. ., τ.-., becomes. These courgettes

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Settlements can of course also occur with less water. In the form of concentrates to be diluted or without water in the form of powders, granules, tablets or other products to be dissolved.

1 2 3 4th 5 6th 7th 8th 9 10 11 12th Chelate
EDDHA / Fe 0.1 0.1 0.1 0.1 0.04 0.04 ο, οβ 0.06 Chelate
EDDHMA / Fe 0.1 mm 0.1 0.1 0.05 Chelate
EDTA / Zn (a 0.1 0.1 0.1 0.1 0.1 0.04 0.02 0.06 ο, οβ 0.06 Chelate
EDTA / Mn 0.1 0.1 0.1 0.1 0.1 0.04 0.02 0.05 ο, οβ ο, οβ Chelate
EDTA / Cu _ - - 0.02 0.01 0.03 0.03 0.03 Boric acid - - - - ■ - - - - - 0.04 0.004 0.004 potassium
nitrate _ 0.03 0.02 0.05 0.05 0.05 urine
material mm 0/35 0.05 0.05 M- Stabili
sator A 0.03 0.02 0.03 0 £ 3 0.02 0.01 0.01 0.02 mm Stabili
sator B 0.05 _- 0.02 0.03 Stabili
Sator C - - - 0p4 - - - - - - - -

(a) The abbreviation EDTA denotes the disodium salt of ethylenediaminetetraacetic acid.

Stabilizer A: 2> 2 '^^' - tetrahydroxy-benzophenone Stabilizer B: sodium salt of 2,2'-dihydroxy-4,4'-dimethoxy-

5-sulfo-benzophenones

, Stabilizer C: mixture of 2,2 ', 4,4'-tetrahydroxy-benzophenone

and 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, commercially under the trade name "UVINUL 490" from the aforementioned General Aniline & Film Corporation available.

Examples 13 to 22

For fertilizing plants and for preventive or curative treatment their iron lump chlororsene by irrigation of the soil

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or ^ any other medium that contains the roots Compositions:

The values are based on the percentage by weight, with the remainder on 100 is obtained with water used as a solvent. These compositions can of course also with less water in the form of concentrates to be diluted or without water in the form of powder, granules, tablets or others products to be dissolved are prepared / grounded »

O 13th 0 • 14th 0 ■ 15th 0 H 16 0 m 17th 0 ■ 0 • 18th 0 19th » • • 0 20th ■ 0 1 21 0 ■ 22nd Chelate
EPDHA / Fe , 05 , 05 0, , 05 0, , 05 3 _ 3 _ ,1 5 ■ ,1 3 * - Chelate
EPDHMA / Fe 5 3 3 •at the 3 ■ MM · 9 , 05 9 0, , 05 5 m 8th ,1 3 - 9 ,1 . Diammonium
phosphate 8th , 6 9 , 9 9 , 9 9 , 9 , 9 , 9 8th , 6 , 6 9 , 9 , 9 potassium
nitrate 3 , 6 , 2 , 2 , 2 0 , 2 * ^ , 6 , 6 - , 2 0 * 2 ammonium
nitrate 0 , 5 0 0 0 0 M. 3.5 3.5 0 0 Mixture van
Trace element
ments (b) O, , 3 0 »2 , 2 i2 , 2 , 2 0, 0, 0 , 2 , 2 Stabili
sator A <■ , 02 , 02 m , 01 O ₄ O, , 04 , 02 Stabili
sator B • , 03 « M. M. M. Mt Stabilisa
gate C • • 05 02 m ·! W. 3 »3 OK 02

(b) Such a mixture can, for example, be one of the two be following?

Chelate EDTA / Mn ί 47 Cholate EDTA / Ni: 11 ChQlat EDTA / Zn: 17th Chßlat EDTA / Cu: 5 Sodium borate: 20th

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- 18 - 8.5 * 2058563 Manganese sulfate j 2.0 # Nickel sulfate: 3.0 % Zinc sulfate: 1.0 % Copper sulfate j 20.0 % * Boric acid ι

EDTA (disodium salt) ι 65.5 %, Examples 23 to M

For the treatment of vegetable and fruit crops and crops of Ornamental plants determined by application to the foliage by spraying and usable by dissolving or suspending in water Compositions (the values are given in öew .- #) *

r ? 3 Ki ? 4 ? 5- 40 25th 24 30th -30 31 32 33 25th Chelate
EDDHA / Fe 10 16 Ml - 72 _m . 50 Chelate
EDDHMA / Fe - - 15th 12th - 6th - 30th - 66 - 10 Stabilizer A 6th - - - 10 - 10 - 18th 24 20th Stabilizer B - 8th - - - - 15th - - - - Stabilizer C - - 4th - - - - - - - - PDT (c) VJl - - - - - - - - - - pimethane (d) 1 - - 15th - - - - - - - Carbaryl (e) - 5 7th - - - - - - - - Dinooap (noun) - - 3 _- - - - finely crushed
nert sulfur 20th 16 mm - - - - Zineb (g) - 10 - - - - - - - - - - Chloropropy
• lat (h) 6th 5 - - 65 - - - - - - Lecithin (i) - - 70 _ - - 30th - n-octadecyl
amine (j) ■ M mm - - - 60 55 _ ** Sodium diatearyl
sulfosucolnate (k) W. - - 6th -

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5
8th 24 -25 26th c7 25th 29 - 31 4th 33 34 , Sodium dodecyl
benzenesulfonate
(D
.Sodium oxy-
nine sulfonate
(m)
Monooleate of
Polyethylene
glycol (η) 2
yi 4th
6th 4th
8th 30th
3 - - - 4th
6th - - 65 Fossil pebbles
acid
kaolin 30th 5
54 - - - - - - -

(c) To designate the insecticidal substance 2,2-bis- (4-chlorophenyl) -Ijljl-triehlorethane commonly used abbreviation (commercial product of J.R. Geigy A.G.)

(d) Common name for hexen- (l) -yl-N, N-dimethylcarbamate, a systemic insecticide (Commercial product of J.R. Geigy A.G.).

(e) General Maine for “C-Naphthyl-N-methylcarbamate, an insecticide (Commercial product of Union Carbide Chemicals Co.).

(f) General name for 2 _J 4-DinitrO-6- (2-octyl) -phenyl-crotonate, an acaricidal fungicide (commercial product from Rohm & Haas Co.).

(g) Common name for zinc-i ^ -ethylene-bis-dithiocarbamate, a Fungicide (commercial product of Rohm & Haas Co.).

(h) ' ^{Name used for isopropyl-4,4 I-} dichlorobenzilate, an acaricide (commercial product of JR Geigy AG).

(i) Natural amphoteric surfactant product that too is known under the name phosphatidylcholine (commercial product of Central Soya, U.S.A., under the commercial name "Centrophill IP").

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(j) Cationic surfactant (commercial product of Armor & Co., U.S.A., under the tradename "Armeen 18 D"). ι

(k) Anionic surfactant (commercial product of American Cyanamid Co., U.S.A.).

(1) Anionic surfactant (commercial product of Atlantic Refining Co., U.S.A., under the tradename "Ultrawet K").

(m) Anionic surface-active product (commercial product from Borregaard, Norway, under the commercial name "Vanisperse CB").

(n) Nonionic surface-active product (commercial product of Armor & Co., U.S.A., under the tradename "PEO-100O-MO").

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Claims (1)

Claims 1.) Use of hydroxy-benzophenones of the formula (II) to stabilize ferric complexes of the probable formula where in the formula I and Ri., which are the same or different from one another can each have a hydrogen atom or an alkyl radical 1 to * 5 carbon atoms or a hydroxyalkyl radical with 1 to 2 carbon atoms mean, where R- * and R ^ also together represent an alkyl group with j5 to 6 carbon atoms can, · X- to Xo, which can be the same or different from one another, In each case a hydrogen atom or an alkyl radical with 1 to 12 carbon atoms or a group OH, NOg or CN or a Alkoxy group with 1 to 8 carbon atoms or a chlorine, Bromine or iodine atom or a group COOM or SO-aM or a group λ Λ Λ r \ I / / "» I "» * In which Y ^ represents a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms or a hydroxyalkyl radical with 2 to 4 carbon atoms or an alkanoyl or alkenoyl radical with a maximum of 8 carbon atoms, while Y _{2 represents} a hydrogen atom or an alkyl radical with 1 to h carbon atoms or represents a hydroxyalkyl radical having 2 to 4 carbon atoms, and M and M ^, which can be the same or different from each other, in each case a hydrogen ion or an alkaline cation or a cation of the formula denote in which Y- ,, Yj, and Y ₅ - *, which can be the same or different from one another, each represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms or a hydroxyalkyl radical having 2 to 4 carbon atoms, where Y- * and Y ^ in addition, together with the nitrogen atom to which they are bound, can also represent a pyrrolidino, piperidino, morpholino, 'piperazino or 4-methyl-l-piperazino radical, while in formula II. R is a hydrogen atom or a hydroxyl group or an alkyl means a group with 1 to 8 carbon atoms, R ¹ denotes a hydrogen atom or a chlorine atom or an alkyl radical having 1 to 5 carbon atoms or a group SO-, M, R "is a hydrogen atom or a Chloratora or a Hydroxy - 109824/2301 * ■ i \ group or an alkyl radical with 1 to 5 carbon atoms or denotes an alkoxy group with 1 to 8 carbon atoms or a group COOM, • R " ^{1 represents} a hydrogen atom or a chlorine atom or a hydroxyl" group or an alkyl radical with 1 to 5 carbon atoms or an alkoxy group with 1 to 8 carbon atoms and R is a hydrogen atom or an alkyl radical having 1 to 5 carbon atoms means and M has the meaning given above with regard to formula I. 2.) Composition with a content of one or more perric complexes according to claim 1, together with a stabilizer, characterized in that the stabilizer comprises one of the hydroxybenzophenones according to claim 1 and this in an amount of ■ 0.2 to 10 %, based on the weight of the perric complex (s), 3 ·) Composition according to claim 2, characterized in that the ferric complex or complexes JLn in an amount of 0.01 to about 80 wt .- ^, if it is a solid composition, and from 0.01 to about 20 wt. 56 if it is an impure liquid composition acts, exists or exists k ") A composition according to claim 2 or> characterized gekennzeich-% net, that the remainder of the composition, if such is present, consisting essentially of one or more products of the class of fertilizers, insecticides, fungicides, nematocides, bactericides, surface active agents , Compounds that provide the plants with trace elements, and solubilizers * that dissolve the solid composition in water. '' are able to favor, this remainder in the case of liquid compositions can consist entirely or partially of water. 5 ·) Use according to claim 1 or composition according to one of claims 2 to 4, characterized in that in the formula., IX ₁ to Xg are chosen such that the two aromatic Parts of the molecule are symmetrical. 6.) Use according to claim 1 or composition according to any one of claims 2 to 5> characterized in that in the formula I X to Xg represent hydrogen atoms and / or methyl radicals. 7.) Use according to claim 1 or composition according to one of claims 2 to 6, characterized in that in the formula I Ri * Ro * R- * and R4 hydrogen atoms and / or methyl or ethyl radicals represent. . 8.) Use according to claim 1 or composition according to one of claims 2 to 6, characterized in that in the formula I R-, and Rj | together represent a tetramethylene group and R. and R _{g are} hydrogen atoms. 9.) Use according to claim 1 or composition according to one of claims 2 to 7 * characterized in that the used Ferric complex or one of the ferric complexes used from 1,2-bis (2-hydroxy-oil-carboxy-benzylamino) -ethane in the form of Sodium, potassium, ammonium, diethylamine, diethanolamine or Morpholine salt is present. 10.) Use according to claim 1 or composition according to one of claims 2 to 7 * characterized in that the used Ferric complex or one of the ferric complexes used from l ^ -Bis - ^ - hydroxy-S-methyl-c ^ -carboxybenzylaminoJ-ethane in the form the sodium, potassium, ammonium, diethylamine, diethanolamine or morpholine salt is present. Ϊ1.) Use according to claim 1 or composition according to one of claims 2 to 7> characterized in that the used Ferric complex or at least one of the ferric complexes used from one of the following acids in the form of sodium, potassium, Ammonium, diethylamine, diethanolamine or morpholine salt is present: 109824/230 1,2-bis- (2-hydroxy-3-methy1- Φ -carboxy-benzylamino) -ethane t, 2-Bls- (2-hydroxy-4-methyl- oL-carboxy-benaylamino) -ethane l, 2- Bis (2-hydroxy-3 # 5-dimethyl-d-carboxy-benzylamino) -ethane. 12.) Use according to claim 1 or composition according to one of claims 2 to 5 * characterized in that the used Ferric complex or at least one of the ferric complexes used from one of the following acids in the form of sodium, Potassium, ammonium, diethylamine, diethanolamine or morpholine salt is available: 1,2-bis (2-hydroxy-5-tert-butyl-ciC-oarboxy-benzylamino) -ethane 1,2-bis (2-hydroxy-5-octyl-oUcarboxy-benzylamino) -ethane Jj l ₁ 2-bis (5-chloro-2-hydroxy-oC-carboxy-benzylamino) -ethane l, 2-bis- (5-bromo-2-hydroxy-oC-carboxy-benzylamino) -ethane i, 2- Bis- (3 _f 5-dichloro-2-hydroxy- oC-carboxy-benzylamino) -ethane 1,2-bis- (3,5-dibromo-2-hydroxy- oC-carboxy-benzylamino) -ethane l, 2- Bis- (2-hydroxy-5-iodo-oC-carboxy-benzylamino) -ethane Ij 2-bis- (5-carboxy-2-hydroxy-o ( _J -carboxy-benzylamino) -ethane I, 2-bis- (.5-cyano-2-hydroxy- oC-carboxy-benzylamino) -ethane 1,2-bis- (2,4-dihydroxy- oC-carboxy-benzyl.amino) -ethane 1,2-bis - (^ - hydroxy-S-sulfo-oC-carboxy-benzylamino) -ethane 1,2-bis - ^ - hydroxy-S-nitro-oC-carboxy-benzylamino) -ethane 1,2-bis- (2-hydroxy-4- methoxy-o ( _/ -carboxy-benzylamino) -ethane 1,2-bis- (2-hydroxy-4-hexyloxy-oc-carboxy-benzylamino) -ethane λ 1,2-bis- (2-hydroxy- oC- carboxy-benzylamino) -propane t, 2-bis- (2-hydroxy-o6-carboxy-benzylamino) -butane 2, ^ - bis- (2-hydroxy-oil-carboxy-benzylamino) -butane.1, 2 «^ J ₇ -. ;-( l. ¹ -hydro: 'C; / - ci ~ o'-ir'ooxy-ben3yl-iifiino) ~ 4 ~ hydroxy-butane. 13 * 5 Use according to claim 1 or composition na ch one of claims 2 to 5 or according to claim 8, characterized in that the ferric complex used or one of the ferric complexes used of 1,2-bis (2-hydroxy-o £ -carboxy ~ benzylamino) -oyclohexane in the form of sodium , Potassium, ammonium, diethyl, diethanolamine or morpholine salt is present. ι 1Q982A / 2301 - 2ο - 14.) Use according to claim 1 or composition according to one of claims 2 to 13, characterized in that the hydroxybenzophenone is one of the following: 2-hydroxy-benzophenone 2,2 ', 4,4'-tetrahydroxy-benzophenone 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone 2-hydroxy-4-methoxy-benzophenone 2,4-dihydroxy-benzophenone 2,2'-dihydroxy -4,4'-dimethoxy-5-sulfo-benzophenone 2-hydroxy-4-methoxy-5-sulfo-benzophenone 5-chloro-2-hydroxy-benzophenone 2,2'-dihydroxy-benzophenone 2,2'-dihydroxy 4-methoxy-benzophenone 2-hydroxy-4-methoxy-4'-methy1-benzophenone 2-hydroxy-5-methy1-benzophenone 2,4,4'-trihydroxy-benzophenone 2-hydroxy-4'-methy1-benzophenone 2- Hydroxy-4'-ethy1-benzophenone 2,4-dihydroxy-4'-methy1-benzophenone 2,4-dihydroxy-4'-methoxy-benzophenone 2,4-dihydroxy-4'-ethy1-benzophenone 2,4-dihydroxy 4'-oetyloxy-benzophenone 2,2'-dihydroxy-4-octyloxy-benzophenone 2,2'-dihydroxy-3-methy1-benzophenone 2,4-dihydroxy-2'-carboxy-benzophenone (sodium salt) 2,2 '- Dihydroxy -41-chloro-benzophenone 2,2 ^f -dihydroxy-5-chloro-4,4'-dimethoxy-benzophenone. 15 ·) Use according to claim 1 or composition according to one of claims 2 to 14, characterized in that the proportion of hydroxy-benzophenone 0.2 to 2 parts., Based on the Weight of ferric complex present in the composition. 16.) Composition according to one of claims 2 to 15, characterized characterized as containing a lower alkenol. 109824/2301